EP3075765B1 - Hydrophilically modified fluorinated membrane - Google Patents

Hydrophilically modified fluorinated membrane Download PDF

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Publication number
EP3075765B1
EP3075765B1 EP15196329.5A EP15196329A EP3075765B1 EP 3075765 B1 EP3075765 B1 EP 3075765B1 EP 15196329 A EP15196329 A EP 15196329A EP 3075765 B1 EP3075765 B1 EP 3075765B1
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Prior art keywords
copolymer
polymer
membrane
formula
porous
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German (de)
English (en)
French (fr)
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EP3075765A1 (en
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Khaled Abdel-Hakim Helmy Aamer
Jian Qiu
Hassan Ait-Haddou
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Pall Corp
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Pall Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/30—Polyalkenyl halides
    • B01D71/32—Polyalkenyl halides containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0006—Organic membrane manufacture by chemical reactions
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/10—Supported membranes; Membrane supports
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    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/10—Supported membranes; Membrane supports
    • B01D69/106—Membranes in the pores of a support, e.g. polymerized in the pores or voids
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D69/107—Organic support material
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    • B01D69/12—Composite membranes; Ultra-thin membranes
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    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
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    • B01D71/06—Organic material
    • B01D71/44—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of groups B01D71/26-B01D71/42
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    • B01D71/06—Organic material
    • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • B01D71/80—Block polymers
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
    • C08F232/08—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
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    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
    • C08J5/2218—Synthetic macromolecular compounds
    • C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
    • C08J5/2237—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds containing fluorine
    • C—CHEMISTRY; METALLURGY
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    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/056—Forming hydrophilic coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/36—After-treatment
    • C08J9/365—Coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/02—Hydrophilization
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/30—Cross-linking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/24—Mechanical properties, e.g. strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/36—Hydrophilic membranes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2427/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2465/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers

Definitions

  • fluoropolymer membranes for example, porous PTFE membranes, including their mechanical strength, chemical resistance or inertness, non-adhesiveness, excellent dielectric property, thermal stability at high temperature and low coefficient of friction make them very attractive for various applications.
  • it will be beneficial to modify the surface of PTFE without affecting its intrinsic properties. Efforts have been made to modify the surface and the chemical properties of PTFE membrane in order to improve the suitability of the membrane for specific applications.
  • the invention provides a composite hydrophilic porous membrane comprising a porous fluoropolymer support and a coating comprising a copolymer, wherein the copolymer comprises repeat units A and B, wherein A is selected from and B is of the formula wherein n and m are from 1 to about 1000, provided the sum of n and m is equal to or greater than 10.
  • the invention further provides a composite hydrophilic porous membrane comprising a porous fluoropolymer support and a coating comprising a polymer having one or more perfluoroalkylthio pendant groups attached to the backbone of the polymer, whose repeat units are of the formula: wherein * indicates the point of attachment of the perfluoroalkylthio pendant group.
  • copolymers and the polymers having perfluoroalkylthio pendant groups are useful in modifying the surface of porous fluoropolymer supports.
  • the present invention further provides methods of preparing the copolymers and the polymers having perfluoroalkylthio pendant groups, and methods of preparing hydrophilically modified fluoropolymer porous membranes.
  • the invention further provides methods of filtering fluids through these porous membranes.
  • the invention provides a composite hydrophilic porous membrane comprising a porous fluoropolymer support and a coating comprising a copolymer, wherein the copolymer comprises repeat units A and B, wherein A is selected from and B is of the formula wherein n and m are from 1 to about 1000, provided the sum of n and m is equal to or greater than 10.
  • dotted lines on the formulas of the repeat units indicate that the copolymer can be a block copolymer or a random copolymer.
  • Block copolymer are indicated by parentheses: (repeat unit).
  • Random copolymers are indicated by square brackets: [repeat unit].
  • n and m represent the degrees of polymerization of the respective monomers, and are independently from about 10 to about 1000, preferably from about 20 to about 50.
  • n and m represent the mole fraction of the monomers present in the copolymer and n and m can independently range between 1 to 99 mole %, preferably 20 to 50 mole %.
  • the respective monomer blocks can be present in the block copolymer in any suitable mass %, for example, in an embodiment, from about 99%: about 1% to about 50%: about 50%, preferably from about 90%: about 10% to about 70%: about 30%, and more preferably from about 75%: about 25%.
  • the copolymer could be a block copolymer or a random copolymer.
  • the block copolymer could be a diblock (A-B), triblock (A-B-A or B-A-B), or multiblock copolymer ((A-B)x).
  • the copolymer can have a third segment C, for example, a triblock copolymer or a random copolymer such as A-B-C.
  • the copolymer can be of any suitable molecular weight, for example, in an embodiment, a number or weight (Mn or Mw) average molecular weight from about 10 kDa to about 1000 kDa, preferably from about 75 kDa to about 500 kDa, and more preferably from about 250 kDa to about 500 kDa.
  • Mn or Mw number or weight
  • the copolymer of the invention has one of the following formulae:
  • the copolymer of the invention further comprises one or more repeat units C of the formula: wherein the ratio o/(m+n) is from above 0 to about 0.25, preferably from about 0.05 to about 0.25, and more preferably from about 0.10 to about 0.15, mole %.
  • the copolymer has the following formula:
  • the present invention further provides a composite hydrophilic porous membrane comprising a porous fluoropolymer support and a coating comprising a polymer, wherein the polymer has one or more perfluoroalkylthio pendant groups attached to the backbone of the polymer whose repeat unit is of the formula: wherein * indicates the point of attachment of the perfluoroalkylthio pendant group.
  • the perfluoroalkylthio pendant group can be present in some or all of the repeat units of the polymer.
  • the perfluoroalkylthio pendant group can be present in an amount above 0 to 100%, and in embodiments, from about 1 to about 50% or from about 10 to about 30%, of the repeat units.
  • the perfluoroalkylthio pendant group is located randomly in the backbone of the polymer.
  • copolymers and the polymers having pendant perfluoroalkylthio groups of the invention can be prepared by any suitable method, for example, through ring opening metathesis polymerization (ROMP) of cyclic monomers.
  • ROMP ring opening metathesis polymerization
  • a transition metal catalyst containing a carbene ligand mediates the metathesis reaction.
  • ROMP catalyst any suitable ROMP catalyst can be used, for example, Grubbs' first, second, and third generation catalysts, Umicore, Hoveyda-Grubbs, Schrock, and Schrock-Hoveyda catalysts can be employed.
  • Grubbs' first, second, and third generation catalysts Umicore, Hoveyda-Grubbs, Schrock, and Schrock-Hoveyda catalysts can be employed.
  • Umicore Hoveyda-Grubbs
  • Schrock Schrock-Hoveyda catalysts
  • Schrock-Hoveyda catalysts examples include the following:
  • Grubbs' third generation catalysts are particularly suitable due to their advantages such as stability in air, tolerance to multiple functional groups, and/or fast polymerization initiation and propagation rates.
  • the end groups can be engineered to accommodate any compatible groups, and the catalyst can be recycled readily.
  • a preferred example of such a catalyst is:
  • the above third generation Grubbs catalyst (G3) may be obtained commercially or prepared from a Grubbs second generation catalyst (G2) as follows:
  • the present invention further provides a method for preparing the copolymers and polymers having pendant perfluoroalkylthio groups.
  • the invention provides a method of preparing a block copolymer having segment A selected from: the method comprising:
  • copolymer prepared from cis-5-oxanorbornene-exo-2,3-dicarboxylic anhydride (Poly(C2-b-PNF6)) can be reacted with an aqueous base to obtain a copolymer having segment A with dicarboxylic acid,
  • the present invention further provides a method of preparing a random copolymer of the invention, comprising polymerizing (i) a mixture of dimethyl ester of cis-5-norbornene-exo-2,3-dicarboxylic acid and 5-(perfluorohexyl)norbornene catalyzed by a ROMP catalyst or (ii) a mixture of dimethyl ester of cis-5-oxanorbornene-exo-2,3-dicarboxylic acid, 5-(perfluorohexyl)norbornene, and N-mercaptoethyl cis-5-norbornene-exo-2,3-dicarboxylimide catalyzed by a ROMP catalyst.
  • the present invention further provides a method of preparing the polymer having perfluoroalkylthio pendant groups, comprising (i) polymerizing a monomer selected from cis-5-oxanorbornene-exo-2,3-dicarboxylic anhydride, dimethyl ester of cis-5-norbornene-exo-2,3-dicarboxylic acid, and dimethyl ester of cis-5-oxanorbornene-exo-2,3-dicarboxylic acid, catalyzed by a ROMP catalyst to obtain a homopolymer; and (ii) reacting the resulting homopolymer with 1H, 1H, 2H, 2H-perfluorodecanethiol.
  • the polymer prepared from cis-5-oxanorbornene-exo-2,3-dicarboxylic anhydride and modified with 1H, 1H, 2H, 2H-perfluorodecanethiol can be reacted with an aqueous base, for example, sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, and the like, at a suitable concentration, e.g., 0.01N to about 10N, and preferably, from about 0.1N to 1N, to obtain a polymer having a dicarboxylic acid salt thereof which can be neutralized with a mineral acid such as hydrochloric acid, sulfuric acid, or nitric acid, to the dicarboxylic acid form,
  • an aqueous base for example, sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, and the like
  • a suitable concentration e.g. 0.01N to about 10N, and preferably, from about 0.1N to 1N
  • a suitable solvent for example, solvents generally used for conducting ROMP polymerizations.
  • suitable solvents include aromatic hydrocarbons such as benzene, toluene, and xylene, aliphatic hydrocarbons such as n-pentane, hexane, and heptane, alicylic hydrocarbons such as cyclohexane, and halogenated hydrocarbons such as dichloromethane, dichloroethane, dichloroethylene, tetrachloroethane, chlorobenzene, dichlorobenzene, and trichlorobenzene, as well as mixtures thereof.
  • the monomer concentration can be in the range of 1 to 50 wt%, preferably 2 to 45 wt%, and more preferably 3 to 40 wt %.
  • the polymerization can be carried out at any suitable temperature, for example, from -20 to +100 °C, preferably 10 to 80 °C.
  • the polymerization can be carried out for any time suitable to obtain the appropriate chain length of each of the blocks, which can be from about 1 minute to 100 hours.
  • the amount of catalyst can be chosen in any suitable amount.
  • the molar ratio of the catalyst to the monomer can be about 1:10 to about 1:1000, preferably about 1:50 to 1:500, and more preferably about 1:100 to about 1:200.
  • the molar ratio of the catalyst to the monomer could be 1:n and 1:m, where n and m are the average degrees of polymerization.
  • the polymers can be isolated by a suitable technique, for example, precipitation with a nonsolvent.
  • the copolymer and the polymer having perfluoroalkylthio pendant groups of the invention can be characterized for their molecular weights and molecular weight distributions by any known techniques.
  • a MALS-GPC technique can be employed. The technique uses a mobile phase to elute, via a high pressure pump, a polymer solution through a bank of columns packed with a stationary phase. The stationary phase separates the polymer sample according to the chain size followed by detecting the polymer by three different detectors.
  • a series of detectors can be employed, e.g., an Ultraviolet detector (UV-detector), followed by a multi-angle laser light scattering detector (MALS-detector), which in turn, is followed by a refractive index detector (RI-detector) in a row.
  • UV-detector measures the polymer light absorption at 254 nm wavelength
  • MALS-detector measures the scattered light from polymer chains relative to mobile phase.
  • copolymers and polymers having perfluoroalkylthio pendant groups of the invention are highly monodisperse.
  • the copolymers have an Mw/Mn of 1.05 to 1.5, preferably 1.1 to 1.2.
  • the invention provides a method for preparing a copolymer of the formula:
  • the present invention further provides a method for preparing Poly(C2 diacid-b-NPF6) comprising hydrolyzing Poly(C2-b-PNF6) with an aqueous base, as illustrated below:
  • the present invention further provides a method for preparing Poly(C3-b-NPF6), comprising:
  • the present invention further provides a method for preparing copolymer Poly(C4-b-NPF6) comprising:
  • the present invention further provides a method for preparing a copolymer Poly(C3-r-NPF6) comprising polymerizing a mixture of dimethyl ester of cis-5-norbornene-exo-2,3-dicarboxylic acid and 5-(perfluorohexyl)norbornene catalyzed by a ROMP catalyst.
  • the present invention further provides a method of preparing a random copolymer of the formula comprising polymerizing a mixture of dimethyl ester of cis-5-oxanorbornene-exo-2,3-dicarboxylic acid, 5-(perfluorohexyl)norbornene, and N-mercaptoethyl cis-5-norbornene-exo-2,3-dicarboxylimide catalyzed by a ROMP catalyst.
  • the present invention further provides a method for preparing a polymer of the formula comprising polymerizing dimethyl ester of cis-5-norbornene-exo-2,3-dicarboxylic acid and 5-(perfluorohexyl)norbornene catalyzed by a ROMP catalyst and reacting the resulting polymer with 1H, 1H, 2H, 2H-perfluorodecanethiol, as illustrated below:
  • polymerization can be terminated in a suitable manner, for example, by the use of alkyl vinyl ether such as ethyl vinyl ether.
  • alkyl vinyl ether such as ethyl vinyl ether.
  • the other of the end groups can be provided by choosing an appropriate ROMP catalyst.
  • a phenyl end group can be provided by the use a ROMP catalyst having a benzylidenyl group on the transition metal.
  • the present invention further provides a composite hydrophilic porous membrane comprising a porous fluoropolymer and a copolymer or polymer as described above, wherein the copolymer or polymer is optionally crosslinked.
  • the present invention further provides a method of hydrophilically modifying a porous fluoropolymer support comprising:
  • Fig. 1 illustrates a process for coating the porous fluoropolymer support with a copolymer in accordance with an embodiment of the invention.
  • Fig. 2 illustrates a method of crosslinking the coating on a porous fluoropolymer support in accordance with an embodiment of the invention.
  • Crosslinking can be carried out by any suitable method, for example, by the use of a photoinitiator and a high energy radiation, e.g., UV. It is contemplated that the crosslinking would provide a highly stable polymer network in the membrane.
  • photoinitiator can be used, for example, Type I and Type II photoinitiators.
  • photoinitiators include camphor quinone, benzophenone, benzophenone derivatives, acetophenone, acetophenone derivatives, phosphine oxides and derivatives, benzoin alkyl ethers benzil ketals, phenylglyoxalic esters and derivatives thereof, dimeric phenylglyoxalic esters, peresters, halomethyltriazines, hexaarylbisimidazole /coinitiators systems, ferrocenium compounds, titanocenes, and combinations thereof.
  • the crosslinking can be carried out as follows.
  • the polymer coated PTFE sheets are optionally pre-wet with IPA, the sheets are then washed with the solvent with which the photo-initiator is prepared in to exchange IPA with that solvent.
  • the sheets are then soaked in a solution of photo-initiator with certain concentration for a certain time followed by exposure to UV irradiation.
  • the soaking time in photo-initiator solution ranges from 1 minute to 24 hours.
  • the UV irradiation time ranges from 30 seconds to 24 hours.
  • the membrane critical wetting surface tension (CWST), performance characterization, and/or SPM testing are then measured.
  • “SPM” means hot sulfuric acid hydrogen peroxide mixture (H 2 SO 4 (96%): H 2 O 2 (30%) of 80:20 by volume) at 120 to 180 °C.
  • the hydrophilic fluoropolymer membrane is a porous membrane, e.g., a nanoporous membrane, for example, a membrane having pores of diameter between 1 nm and 100 nm, or a microporous membrane having pores of diameter between 1 ⁇ m and 10 ⁇ m.
  • the surface tension of the resulting porous membrane can be determined as follows. For example, a sheet of PTFE porous support is coated at room temperature by pre-wetting the membrane sheet with IPA solvent and soaking the membrane in a coating polymer solution with concentration that ranges between 0.1% and 10% by mass. The coating time ranges between (1 min to 12 hours). After soaking the support, it is dried in convection oven at 100 °C to 160 °C. The drying time ranges between (10 minutes to 12 h). The resulting porous PTFE membrane's wetting characteristics are measured by measuring the critical wetting surface tension.
  • the change in surface modification in terms of surface tension was measured by measuring the critical wetting surface tension (CWST).
  • CWST critical wetting surface tension
  • the method relies on a set of solutions of certain composition. Each solution has specific surface tension. The solution's surface tension ranges from 25 to 92 dyne/cm in small non-equivalent increments.
  • the membrane surface tension To measure the membrane surface tension, the membrane is positioned on to top of white light table, one drop of a solution of certain surface tension is applied to the membrane surface and the time the drop takes to penetrate through the membrane and become bright white as an indication of light going through the membrane is recorded. Instant wetting is considered when the time the drop takes to penetrate the membrane is ⁇ 10 seconds. If the time > 10 seconds, the solution is considered to partially wet the membrane.
  • Hydrophilic fluoropolymer porous membranes can be used in a variety of applications, including, for example, diagnostic applications (including, for example, sample preparation and/or diagnostic lateral flow devices), ink jet applications, lithography, e.g., as replacement for HD/UHMW PE based media, filtering fluids for the pharmaceutical industry, metal removal, production of ultrapure water, treatment of industrial and surface waters, filtering fluids for medical applications (including for home and/or for patient use, e.g., intravenous applications, also including, for example, filtering biological fluids such as blood (e.g., virus removal)), filtering fluids for the electronics industry (e.g., filtering photoresist fluids in the microelectronics industry and hot SPM), filtering fluids for the food and beverage industry, beer filtration, clarification, filtering antibody- and/or protein-containing fluids, filtering nucleic acid-containing fluids, cell detection (including in situ ), cell harvesting, and/or filtering
  • diagnostic applications including,
  • porous membranes according to embodiments of the invention can be used to filter air and/or gas and/or can be used for venting applications (e.g., allowing air and/or gas, but not liquid, to pass therethrough).
  • Porous membranes according to embodiments of the inventions can be used in a variety of devices, including surgical devices and products, such as, for example, ophthalmic surgical products.
  • the hydrophilic fluoropolymer porous membrane can have a variety of configurations, including planar, flat sheet, pleated, tubular, spiral, and hollow fiber.
  • Hydrophilic fluoropolymer porous membranes are typically disposed in a housing comprising at least one inlet and at least one outlet and defining at least one fluid flow path between the inlet and the outlet, wherein at least one inventive membrane or a filter including at least one inventive membrane is across the fluid flow path, to provide a filter device or filter module.
  • a filter device comprising a housing comprising an inlet and a first outlet, and defining a first fluid flow path between the inlet and the first outlet; and at least one inventive membrane or a filter comprising at least one inventive membrane, the inventive membrane or filter comprising at least one inventive membrane being disposed in the housing across the first fluid flow path.
  • At least one inventive porous membrane or filter comprising at least one inventive membrane is disposed in a housing comprising at least one inlet and at least two outlets and defining at least a first fluid flow path between the inlet and the first outlet, and a second fluid flow path between the inlet and the second outlet, wherein the inventive membrane or filter comprising at least one inventive membrane is across the first fluid flow path, to provide a filter device or filter module.
  • the filter device comprises a crossflow filter module, the housing comprising an inlet, a first outlet comprising a concentrate outlet, and a second outlet comprising a permeate outlet, and defining a first fluid flow path between the inlet and the first outlet, and a second fluid flow path between the inlet and the second outlet, wherein at least one inventive membrane or filter comprising at least one inventive membrane is disposed across the first fluid flow path.
  • the filter device or module may be sterilizable. Any housing of suitable shape and providing an inlet and one or more outlets may be employed.
  • the housing can be fabricated from any suitable rigid impervious material, including any impervious thermoplastic material, which is compatible with the fluid being processed.
  • the housing can be fabricated from a metal, such as stainless steel, or from a polymer, e.g., transparent or translucent polymer, such as an acrylic, polypropylene, polystyrene, or a polycarbonate resin.
  • the hydrophilic fluoropolymer porous membrane comprises any suitable porous fluoropolymer support, for example, a support made from PTFE, PVDF (polyvinylidene fluoride), PVF (polyvinyl fluoride), PCTFE (polychlorotrifluoroethylene), FEP (fluorinated ethylene-propylene), ETFE (polyethylenetetrafluoroethylene), ECTFE (poly ethylenechlorotrifluoroethylene), PFPE (perfluoropolyether), PFSA (perfluorosulfonic acid), and perfluoropolyoxetane.
  • the porous support can have any suitable pore size, e.g., from about 2 nm to about 10 microns, preferably PTFE and PVDF.
  • the present invention further provides a hydrophilically modified fluoropolymer porous membrane produced by the method described above.
  • the present invention further provides a method of filtering a fluid, the method comprising passing the fluid through the hydrophilic fluoropolymer porous membranes described above.
  • Dimethyl 5-norbornene-2,3-dicarboxylate (C3) was purchased from Alfa Aesar,
  • Dichloromethane was stored over activated Alumina and purged with Argon before use, Isopropyl alcohol (IPA), dicyclopentadiene (DCPD), 1H,1H,2H-Perflouro-1-octene (PF6), 1H,1H,2H-Perflouro-1-dodecene (PF10), toluene, thionyl chloride, ethylacetate, dimethylformamide (DMF), Maleimide, furan, diisopropylazodicarboxylate (DIAD), triphenylphosphine (Ph 3 P), 1-haxadecanol, tetrahydrofuran (THF), ethyl acetate, N-phenylmaleimide, acetonitrile, methanol, Grubbs second generation catalyst, 3-bromopyridine, and pentane were obtained from Sigma-Aldrich Co.
  • IPA Isopropyl alcohol
  • DCPD
  • This example illustrates the preparation of dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene](benzylidene)bis(3-bromopyridine)ruthenium(II) (G3) catalyst.
  • the second generation Grubbs catalyst (G2) illustrated above (1.0 g, 1.18 mmol) was mixed with 3-bromopyridine (1.14 mL, 11.8 mmol) in 50 mL flask. Upon stirring at room temperature for 5 min, the red mixture turned into bright green. Pentane (40 mL) was added with stirring for 15 minutes and green solid was obtained. The mixture was cooled in the freezer for 24 h and filtered under vacuum. The resulting G3 catalyst, a green solid, was washed with cold pentane and dried under vacuum at room temperature to give a yield of 0.9 g, 88% yield.
  • This example illustrates the gel permeation chromatographic characterization of the homopolymer and copolymers in accordance with an embodiment of the invention.
  • This example illustrates a procedure to prepare NPF6 monomer in accordance with an embodiment of the invention.
  • a Parr high pressure reactor cylinder vessel was charged with DCPD (100 ml, 737 mmol), PF6 (168 ml, 737 mmol) and the cylinder was attached to the reactor, and hydroquinone (2.43 g, 22.1 mmol), heated to 170 °C for 72 hours.
  • the reaction content was dissolved into 150 ml DCM and transferred into 500 ml round bottom flask to purify the monomer by vacuum distillation.
  • This example illustrates a procedure to prepare NPF10 monomer in accordance with an embodiment of the invention.
  • a Parr high pressure reactor cylinder vessel was charged with DCPD (24.6 ml, 183 mmol), PF6 (132 ml, 370 mmol) and the cylinder was attached to the reactor, and hydroquinone (1.08 g, 10 mmol), heated to 170 °C for 72 hours.
  • the reaction content was dissolved into 150 ml DCM and transferred into 500 ml round bottom flask to purify the monomer by vacuum distillation.
  • This example illustrates a procedure to prepare C2 monomer in accordance with an embodiment of the invention.
  • This example illustrates a procedure to prepare a C4 monomer, which is a dimethyl ester of the C2 monomer, in accordance with an embodiment of the invention.
  • exo-7-oxanorbornene-5.6-dicarboxyanhydride (C2) (65 g, 0.4 mol) was dissolved in methanol (750 ml), thionyl chloride (25 ml) was added to the C2 solution slowly drop wise to form a yellow solution. The solution was refluxed for 48 hours after which the solvent was removed till dryness and to obtain the monomer. The solid was dissolved in ethyl acetate, washed with K 2 CO 3 solution (200 ml, 2x), washed with DI water (200 ml, 2x) and dried over MgSO 4 . The resulting yellow solution was concentrated to give the C4 monomer.
  • This example illustrates a procedure to prepare N-2-Mercapto-Ethyl-Norbornene-Dicarboximide (NHS).
  • norbornene-5.6-dicarboxyanhydride 25 g, 1.5 mol was dissolved in toluene (300 ml), aminoethanethiol (14 ml, 1.83 mol) was added to the solution slowly drop wise.
  • a Dean-Stark trap was attached to a condenser attached to an RBF to collect the water formed during the reaction.
  • the solution was refluxed for 24 hours after which the solvent was removed from the yellow solution till dryness and to obtain the monomer.
  • the resulting solid was dissolved in ethylacetate, washed with K 2 CO 3 solution (200 ml, 2x), washed with DI water (200 ml, 2x) and dried over MgSO 4 .
  • the resulting yellow solution was concentrated to give the monomer.
  • This example illustrates the synthesis and properties of copolymer Poly(C2-b-NPF6) in accordance with an embodiment of the invention.
  • Grubbs 3 rd generation (G3) catalyst 22 mg, 0.025 mmol was weighed in 40 mL vial with equipped with fluoropolymer resin-silicone septa open-top cap. G3 was dissolved in Argon degassed THF (60 mL) and transferred via cannula to clean 1L RBF equipped with stirring bar. A solution of C2 monomer (3.05 g, 18.4 mmol) in THF (86 mL) was degassed with Argon gas and transferred into the G3 solution and stirred for 30 minutes.
  • NPF6 monomer (1.03 g, 2.5 mmol) in THF (208 mL) was degassed with Argon gas and transferred into the growing Poly(C2) block solution and was stirred for another 60 minutes. Ethylvinylether (2mL) was then added to the yellow solution of the diblock copolymer to terminate the reaction. The polymer was precipitated in MeOH (2 L, 2x) to recover the white solid of pure polymer. The resulting polymer was filtered and dried under vacuum at room temperature, yield (4.0 g, 98%).
  • Elemental Analysis data are set forth in Table 1 below. Table 1. Elemental Analysis Polyme r Acrony m Element al Analysis Theoretical (w%) Actual (w%) F-block w% Hydro -philic w% Mole % C% H% F% C% H% F% F-block % Hydro-philic% Poly(C2 -b-NPF6)-1 C, H, F 49.68 % 4.12 % 12.25 % 80% 9% 91% Poly(C2 -b-NPF6)-2 C, H, F 48.02 % 4.45 % 3.05 % 20% 95% 2% 98%
  • the Poly(C2-b-NPF6)-1 copolymer was dissolved in THF to provide a 1% by wt solution.
  • a PTFE microporous support (KA-N3P72) sample was immersed in the polymer solution for 1 hr. The PTFE sample was air dried for 10 minutes, followed by 30 min of washing in THF. The sample was again air dried for 10 minutes.
  • the CWST of the coated PTFE membrane was measured to be 33.41 dyne/com.
  • the CWST of the starting PTFE membrane was 25.4 dyne/cm.
  • This example demonstrates the synthesis and properties of another copolymer Poly(C3-b-NPF6) in accordance with an embodiment of the invention.
  • Grubbs 3 rd generation (G3) catalyst 11 mg, 0.012 mmol was weighed in 40 mL vial with equipped with fluoropolymer resin-silicone septa open-top cap. G3 was dissolved in Argon degassed THF (60 mL) and transferred via cannula to clean 1L RBF equipped with stirring bar. A solution of the C3 monomer (2.5 g, 12 mmol) in THF (86 mL) was degassed with Argon gas and transferred into the G3 solution and shirred for 30 minutes.
  • the Poly(C3-b-NPF6)-1 copolymer was dissolved in THF to provide a 1% by wt solution.
  • a PTFE porous support sample was immersed in the polymer solution for 1 hr. The PTFE sample was air dried for 10 minutes, followed by 30 min of washing in THF. The sample was again air dried for 10 minutes.
  • the CWST of the coated PTFE membrane was measured to be 30 dyne/com.
  • the CWST of the starting PTFE support was 25.4 dyne/cm.
  • Poly(C4-b-NPF6) was synthesized as follows.
  • Grubbs 3 rd generation (G3) catalyst 25 mg, 0.028 mmol is weighed in 40 mL vial with equipped with fluoropolymer resin-silicone septa open-top cap.
  • G3 was dissolved in Argon degassed THF (60 mL) and transferred via cannula to clean 1L RBF equipped with stirring bar.
  • a solution of C4 monomer (2.5 g, 11.8 mmol) in THF (86 mL) was degassed with Argon gas and transferred into the G3 solution and shirred for 30 minutes.
  • NPF6 monomer (0.86 g, 2.0 mmol) in THF (208 mL) was degassed with Argon gas and transferred into the growing Poly(C4) block solution and is stirred for another 60 minutes. Ethylvinylether (2mL) was then added to the yellow solution of the diblock copolymer to terminate the reaction. The polymer was precipitated in MeOH (2 L, 2x) to recover the white solid of pure polymer. The polymer was filtered and dried under vacuum at room temperature, yield (3.0 g, 90%).
  • the GPC trace of the copolymer in CH 2 Cl 2 is shown in Fig. 3 .
  • the Poly(C4-b-NPF6)-1 copolymer was dissolved in THF to provide a 1% by wt solution.
  • a PTFE microporous membrane sample was immersed in the polymer solution for 1 hr. The PTFE sample was air dried for 10 minutes, followed by 30 min of washing in THF. The sample was again air dried for 10 minutes.
  • the CWST of the coated PTFE membrane was measured to be 39 dyne/com.
  • the CWST of the starting PTFE membrane was 25.4 dyne/cm. Table 3.
  • Membrane ID Control HHP-0015-005-BBUV
  • Coated membrane C2-Polymer
  • Water flux L/m 2 /h
  • Water flux (L/m 2 /h) after SPM 207.49 122.61 CWST(Dynes/cm) before SPM 31 79 CWST (Dynes/cm) after SPM 31 42
  • This example demonstrates the synthesis and properties of a polymer having pendant perfluoroalkylthio groups in accordance with an embodiment of the invention.
  • a Poly(C2) homopolymer (1.0 g, 6.0 mmol), 1H,1H,2H-Perflurodecanethiol (3.0 g, 6.0 mmol), and AIBN (79.8 mg) were dissolved in 33 ml of THF and allowed to react at 55 °C for 26 h under nitrogen. The reaction mixture was poured into water. The precipitate obtained was dissolved in THF and precipitated again from heptane to yield a dark brown solid polymer of interest.
  • the polymer having pendant perfluoroalkylthio groups was dissolved in THF to provide a 1% by wt solution.
  • a PTFE microporous support sample was immersed in the polymer solution for 1 hr. The PTFE sample was air dried for 10 minutes, followed by 30 min of washing in THF. The sample was again air dried for 10 minutes.
  • the CWST of the coated PTFE support was measured to be 33.41 dyne/com (triplicate) (35 partial). The CWST of the starting PTFE support was 25.4 dyne/cm.
  • Poly(C2 diacid-b-NPF6) Poly(C2-b-NPF6) was reacted with 0.1N NaOH solution to obtain Poly(C2 diacid-b-NPF6).
  • Poly(C2-b-NPF6) diblock copolymer was dissolved in THF (1% mass) to form homogenous solution. The polymer solution was treated with 0.1 N NaOH solution in water. The mixture was stirred at ambient temperature for 1h followed by precipitation in hexane.
  • Grubbs 3 rd generation (G3) catalyst 11 mg, 0.012 mmol was weighed in 40 mL vial with equipped with fluoropolymer resin-silicone septa open-top cap. G3 was dissolved in Argon degassed DCM (20 mL) and transferred via cannula to clean 250 ml RBF equipped with stirring bar. A solution of C3 monomer (2.5 g, 12 mmol) and NYF6 (0.86 g, 2.0 mmol) mixture dissolved in DCM (90 ml) was degassed with Argon gas and transferred into the G3 solution and shirred for 12 hours at room temperature.
  • Ethylvinylether (2mL) was then added to the yellow solution of the random copolymer to terminate the reaction.
  • the polymer was then passed through a column of basic alumina, silica gel, and Celite to remove the catalyst.
  • the solvent was removed in a rotary evaporator and the resulting polymer was colorless and highly viscous; yield (3.0 g, 90%).
  • This example demonstrates the synthesis and properties of a triblock polymer in accordance with an embodiment of the invention.
  • Poly(C4-r-NPF6-r-NHS) was synthesized by polymerizing a mixture of dimethyl ester of cis-5-oxanorbornene-exo-2,3-dicarboxylic acid, 5-(perfluorohexyl)norbornene, and N-mercaptoethyl cis-5-norbornene-exo-2,3-dicarboxylimide catalyzed by a ROMP catalyst.

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US9636641B2 (en) 2017-05-02
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